Yellow anionic disazo dyes

ABSTRACT

The present invention relates to novel yellow anionic dyes, a process for their preparation, certain novel intermediates necessary for their preparation and the use of these dyes for dyeing natural or synthetic materials, in particular, paper. The dyes are of formula (14), (15) or (16) 
                         
in which
     R 1  represents hydrogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or SO 3 H,   R 2  represents SO 3 H or CO 2 H,   R 3  represents hydrogen, C 1 -C 4 alkyl, halogen, hydroxy, C 1 -C 4 alkoxy, carboxy, NH 2  or NHC 1 -C 4 alkyl,   R 3a  represents hydrogen or NH 2  and   A 1  and A 2 , independently of the other, is selected from the group consisting of an acetoacetylated amine, a derivative of barbituric acid, a 2,4,6-triaminopyrimidine derivative, a pyridone derivative, an aminopyrazole or a pyrazolone derivative and a benzoic acid derivative, or A 1  and A 2 , each one independently of the other, represent a certain phenol residue.

This application is a divisional of U.S. application Ser. No.12/006,730, filed Jan. 4, 2008 now U.S. Pat. No. 7,723,494, pending,which is a divisional of U.S. application Ser. No. 10/517,410, now U.S.Pat. No. 7,341,607, which is a 371 of international application No.PCT/EP03/05561, filed May 27, 2003, the contents of which applicationsare incorporated by reference.

The present invention relates to novel yellow anionic dyes, a processfor their preparation, certain novel intermediates necessary for theirpreparation and the use of these dyes for dyeing natural or syntheticmaterials, in particular, paper.

The use of diaminobenzanilides as building blocks for the synthesis ofbisazo dyes and the advantages thereof has been described in Dyes andPigments, 17, 297-302 (1991). On this basis, a number of bisazo orangeand yellow dyes containing pyrazolones and phenolic derivatives ascoupling components have been described, for example, in DE 818,669, DE845,084, DE 2,362,995, GB 28,569, U.S. Pat. No. 2,228,321 and in JP51-11817, whilst further symmetrical bisazo dyes containing1-phenyl-5-amino pyrazoles have also been reported in U.S. Pat. No.5,545,725, whilst U.S. Pat. No. 2,544,087 discloses certainbis-acetoacetanilide derivatives.

However, a requirement exists to provide further anionic dyes especiallyof neutral or greenish yellow shades, which dyes exhibit excellentdegrees of exhaustion with high colour strength, whilst beingsufficiently water-soluble to provide stable aqueous formulationswithout the need for large quantities of solubilizers. Furthermore,dyings obtained should exhibit high degrees of bleed- andlight-fastness, be even- or top-sided and be readily bleachable.

Surprisingly, it has now been found that certain bisazo dyes based ondiaminobenzanilides exhibit excellent effects with respect to thedesired properties.

Accordingly, the invention relates to compounds of the formula

in which

-   R₁ represents hydrogen, substituted or unsubstituted C₁-C₈alkyl,    substituted or unsubstituted C₁-C₈alkoxy or SO₃H,-   R₂ represents SO₃H or CO₂H,-   R₃ and R_(3a) each, independently of the other, represent hydrogen,    a C₁-C₄alkyl group, which may be substituted or unsubstituted,    halogen, hydroxy, substituted or unsubstituted C₁-C₄alkoxy, carboxy,    NH₂ or NHC₁-C₄alkyl and each of the residues-   A₁ and A₂, independently of the other, is derived from a coupling    component selected from the group consisting of    -   an acetoacetylated amine of the formula

in which

-   X₁ represents C₁-C₄alkyl, or phenyl which is unsubstituted or    monosubstituted by C₁-C₄alkyl, C₁-C₄alkoxy or halogen and-   X₂ represents phenyl which is unsubstituted, mono-, di- or    trisubstituted by one or two SO₃H, SO₂NHC₁-C₄alkyl groups which    alkyl groups may be substituted, SO₂C₁-C₄alkyl, C₁-C₄substituted or    unsubstituted alkyl, hydroxy, C₁-C₄alkoxy, halogen, CF₃, NH₂,    NHCOC₁-C₄alkyl, NHCOOC₁-C₄alkyl, NHCONHC₁-C₄alkyl, CO₂H,    CONHC₁-C₄alkyl or NO₂; a 1- or 2-naphthyl residue which is    unsubstituted or substituted by one or two SO₃H, SO₂NHC₁-C₄alkyl,    carboxy, CONHC₁-C₄alkyl, carboxyC₁-C₄alkyl or carboxyaryl groups or    a 5- or 6-membered heterocyclic ring containing 1-3 heteroatoms and    which may be benzannelated and be further substituted by C₁-C₄alkyl,    C₁-C₄alkoxy or halogen and which may be attached to the NH-atom in    formula (2) either via the hetero- or benzo-nucleus, in the case of    benzannelated heterocycles;-   a derivative of barbituric acid of the formula

in which

-   Y represents O, NCN or NCONH₂;-   a 2,4,6-triaminopyrimidine;-   a pyridone derivative of the formula

in which

-   Q₁ represents hydrogen, hydroxy, C₁-C₂alkyl, hydroxyethyl,    2-(C₁-C₂alkoxy)alkyl, C₁-C₂alkoxy, COOH, CONH₂ or COO C₁-C₂alkyl,-   Q₂ represents hydrogen, CN, CONH₂, halogen, SO₃H or C₁-C₂alkyl which    is unsubstituted or substituted by hydroxy, phenyl or SO₃H,-   Q₃ represents hydrogen, phenyl, C₁-C₂alkylphenyl, cyclohexyl or    C₁-C₄alkyl which is unsubstituted or substituted by hydroxy, CN,    C₁-C₂alkoxy or SO₃H and-   Q₄ represents hydrogen or hydroxy;-   an aminopyrazole or a pyrazolone derivative of formula

in which

-   R₄ represents hydrogen, substituted or unsubstituted C₁-C₄alkyl,    C₂-C₄alkenyl, NHCO C₁-C₄alkyl or CO₂H, each-   R₅ and R₆, independently of the other, represent hydrogen, halogen,    C₁-C₄alkyl, SO₃H or CO₂H and-   R₇ represents hydrogen or C₁-C₄alkyl;-   a benzoic acid derivative of formula

in which

-   R₇ represents hydrogen or C₁-C₄alkyl and-   R₈ represents hydrogen or hydroxy or-   A₁ and A₂, each one independently of the other, represent a phenol    residue of the formula

in which

-   R₉ and R₁₀, each one independently of the other, represent hydrogen,    C₁-C₄alkyl, C₁-C₄alkoxy, hydroxy, halogen, NH₂, NHCO C₁-C₄alkyl,    NO₂, SO₃H, CO₂C₁-C₄alkyl or CONHC₁-C₄alkyl groups,-   with the proviso that in compounds of formula

if

-   R₁, R₂, R₃ and R_(3a) each, independently of the others, are    hydrogen or SO₃H, then-   A₁ and A₂ are not both a 1-phenyl or    1-sulphophenyl-3-methyl-5-aminopyrazole residue,    or, if-   R₁, R₂, R₃ and R_(3a) represent hydrogen and-   A₁ is a residue of formula (9) in which-   R₇ represents hydrogen or methyl, then-   A₂ does not represent a 1-phenyl or 1-sulphophenyl-3-methyl- or    3-carboxy pyrazol-5-one residue    or, if-   R₁, R₃ and R_(3a) are hydrogen and R₂ is SO₃H and one of-   A₁ and A₂ represents a 1-sulphophenyl-3-methylpyrazol-5-one residue,    then the other is not a residue of formula (11) in which both-   R₉ and R₁₀ are hydrogen, or if-   A₁ represents a 1-nitrophenyl-, a 1-phenyl- or an unsubstituted    3-methylpyrazol-5-one residue,-   A₂ is not a residue of formula (9) in which R₇ represents hydrogen,    or if-   R₁, R₃ and R_(3a) represent hydrogen, R₂ is CO₂H and-   A₁ represents a residue of formula (9), in which R₇ is hydrogen,-   A₂ is not a residue of formula (2) or formula (7);-   in compounds of the formula

if

-   R₂ represents CO₂H, R₃ represents hydroxy or methoxy and R_(3a)    represents hydrogen,-   A₁ and A₂ do not represent residues of formulae (2) or (7) and,-   in compounds of the formula

if

-   R₂ represents SO₃H and R₃ and R_(3a) both represent hydrogen-   A₁ and A₂ are not both 2,4-dihydroxyphenyl.

In one preferred aspect of the invention, the compounds of formula (1),contain a total number of two, three or four SO₃H and/or CO₂H groups.These sulphonic and/or carboxylic acid groups may be represented either,as written, in the form of the free acid or in the salt form, SO₃Mand/or CO₂M. M is preferably one equivalent of a colourless cation,typically lithium, sodium, potassium, ammonium or the protonated form ofa C₄-C₁₂trialkylamine, C₄-C₁₂diamine, C₂-C₁₂alkanolamine or of apolyglycol amine, conveniently, triethanolamine trisglycol ether, ormixtures of such cationic species.

M as a protonated C₄-C₁₂trialkylamine may, for example, be a protonatedN-ethyl-dimethylamine, N,N-diethylmethylamine, tri-n-propylamine,tri-n-butylamine, tri-isobutylamine, and, preferably, triethylamine ortriisopropylamine.

M as a protonated C₄-C₁₂diamine may, for example, be ethylenediamine, or1,3-diaminopropane, in which one or both nitrogen atoms are additionallysubstituted by one or two C₁-C₄alkyl radicals, preferably methyl orethyl radicals. M is preferably an N,N-dialkylethylenediamine orN,N-dialkyl-1,3-diaminopropane. Illustrative examples are:N-ethylethylenediamine, N,N-dimethylethylenediamine,N,N′-dimethylethylenediamine, N,N-diethylethylenediamine,3-dimethylamino-1-propylamine or 3-diethylamino-1-propylamine. M as aprotonated C₂-C₁₂alkanolamine may be the protonated form of amonoalkanolamine, dialkanolamine, monoalkanolmonoalkylamine,monoalkanoldialkylamine, dialkanolalkylamine or trialkanolamine or amixture of different protonated alkanolamines. Illustrative examplesare: protonated 2-aminoethanol, bis(2-hydroxyethyl)amine,N-(2-hydroxyethyl)dimethylamine, N-(2-hydroxyethyl)diethylamine,N,N-bis(2-hydroxyethyl)ethylamine or tris(2-hydroxyethyl)-amine.

One further preferred class of compounds of formula (1) is that of theformula

in which

-   R₁ represents hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy or SO₃H,-   R₂ represents SO₃H or CO₂H,-   R₃ represents hydrogen, a C₁-C₄alkyl group, halogen, hydroxy,    C₁-C₄alkoxy, carboxy, NH₂ or NHC₁-C₄alkyl,-   R_(3a) represents hydrogen or NH₂ and-   A₁ and A₂ are as defined above.

More preferably, however, in the above compounds of formula (13),

-   R₃ and R_(3a) both represent hydrogen and-   A₁ and A₂, each one independently of the other, is derived from a    coupling component selected from the group consisting of-   an acetoacetylated amine of the formula

in which

-   X₁ represents C₁-C₄alkyl, and-   X₂ represents phenyl, which is unsubstituted, mono-, di- or    trisubstituted by SO₃H, C₁-C₄alkyl, hydroxy, C₁-C₄alkoxy, halogen or    CO₂H;-   barbituric acid or cyanoiminobarbituric acid;-   2,4,6-triaminopyrimidine;-   citrazinic acid;-   a pyridone derivative of the formula

in which

-   Q₁ represents C₁-C₂alkyl,-   Q₂ represents CN, CONH₂ or CH₂SO₃H,-   Q₃ represents C₁-C₂alkyl and-   Q₄ represents hydroxy;-   an aminopyrazole or a pyrazolone derivative of formula

in which

-   R₄ represents C₁-C₄alkyl or CO₂H,-   R₅ represents hydrogen, halogen, C₁-C₄alkyl, SO₃H or CO₂H and-   R₆ represents hydrogen;-   a benzoic acid derivative of formula

in which

-   R₇ represents hydrogen or C₁-C₄alkyl and-   R₈ represents hydrogen or hydroxy or-   A₁ and A₂, each one independently of the other, represent a phenol    residue of the formula

in which

-   R₉ represents hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, hydroxy, halogen or    SO₃H and-   R₁₀ represents hydrogen.

Most preferred compounds of formula (13) are those in which

-   R₁ represents hydrogen, C₁-C₄alkoxy, especially methoxy, or SO₃H,-   R₂ represents SO₃H or CO₂H,-   R₃ and R_(3a) both represent hydrogen and the coupling component A₁    is derived from an acetoacetylated amine of formula (2), barbituric    acid or cyanimino barbituric acid, a pyridone derivative of    formula (4) in which Q₁ represents methyl, Q₂ is CN, CONH₂ or    CH₂SO₃H, Q₃ is ethyl or methyl and Q₄ is hydroxy, a compound of    formula (5) or (7) in which R₄ represents C₁-C₄alkyl, especially    methyl, R₅ represents hydrogen or SO₃H and-   R₆ represents hydrogen, or from salicyclic acid and the coupling    component A₂ is derived from an acetoacetylated amine of formula    (2), whereby, in formula (2), X₁ preferably represents methyl and X₂    preferably represents phenyl, which is monosubstituted by SO₃H or    trisubstituted by SO₃H, methyl and methoxy or A₂ is derived from a    pyridone derivative of formula (4) in which Q₁ represents methyl, Q₂    is CN, CONH₂ or CH₂SO₃H, Q₃ is ethyl and Q₄ is hydroxy or from an    aminopyrazole of formula (5) in which R₄ represents C₁-C₄alkyl,    especially methyl, R₅ represents hydrogen or SO₃H and R₆ represents    hydrogen.

A second preferred class of compounds of formula (1) is that of theformula

in which

-   R₁ represents hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy or SO₃H,-   R₂ represents SO₃H or CO₂H,-   R₃ represents hydrogen, a C₁-C₄alkyl group, halogen, hydroxy,    C₁-C₄alkoxy, carboxy, NH₂ or NHC₁-C₄alkyl,-   R_(3a) represents hydrogen or NH₂ and-   A₁ and A₂ are as defined for formula (1) above.

More preferably, however, in the above compounds of formula (14)

-   R₃ and R_(3a) both represent hydrogen and-   A₁ and A₂, each one independently of the other, is derived from a    coupling component selected from the group consisting of-   an acetoacetylated amine of the formula

in which

-   X₁ represents C₁-C₄alkyl, and-   X₂ represents phenyl, which is unsubstituted, mono-, di- or    trisubstituted by SO₃H, C₁-C₄alkyl, hydroxy, C₁-C₄alkoxy, halogen or    CO₂H;-   barbituric acid or cyanoiminobarbituric acid;-   2,4,6-triaminopyrimidine;-   citrazinic acid;-   an aminopyrazole or a pyrazolone derivative of formula

in which

-   R₄ represents C₁-C₄alkyl or CO₂H,-   R₅ represents hydrogen, halogen, C₁-C₄alkyl, SO₃H or CO₂H and-   R₆ represents hydrogen;-   a benzoic acid derivative of formula

in which

-   R₇ represents hydrogen or C₁-C₄alkyl and-   R₈ represents hydrogen or hydroxy or-   A₁ and A₂, each one independently of the other, represent a phenol    residue of the formula

in which

-   R₉ represents hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, hydroxy, halogen or    SO₃H and-   R₁₀ represents hydrogen.

Most preferred compounds of formula (14) are those in which

-   R₁ represents hydrogen, C₁-C₄alkoxy, especially methoxy, or SO₃H,-   R₂ represents SO₃H or CO₂H,-   R₃ and R_(3a) both represent hydrogen and the coupling component A₁    is derived from an acetoacetylated amine of formula (2), barbituric    acid, cyanoiminobarbituric acid, 2,4,6-triaminopyrimidine,    citrazinic acid, a compound of formula (5) or (7) in which R₄    represents C₁-C₄alkyl, especially methyl, R₅ represents hydrogen or    SO₃H and-   R₆ represents hydrogen or from salicyclic acid, methyl salicyclic    acid, phenol or methyl phenol and the coupling component A₂ is    derived from an acetoacetylated amine of formula (2), whereby, in    formula (2), X₁ preferably represents methyl and X₂ preferably    represents phenyl, which is monosubstituted by SO₃H or, especially,    trisubstituted by SO₃H, methyl and methoxy or A₂ is derived from an    aminopyrazole of formula (5) in which R₄ represents C₁-C₄alkyl,    especially methyl, R₅ represents hydrogen or SO₃H and R₆ represents    hydrogen.

A third preferred class of compounds of formula (1) is that of formula

in which

-   R₁ represents hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy or SO₃H,-   R₂ represents SO₃H or CO₂H,-   R₃ represents hydrogen, a C₁-C₄alkyl group, halogen, hydroxy,    C₁-C₄alkoxy, carboxy, NH₂ or NHC₁-C₄alkyl,-   R_(3a) represents hydrogen or NH₂ and-   A₁ and A₂ are as defined for formula (1) above.

More preferably, however, in the above compounds of formula (15)

-   R₃ and R_(3a) both represent hydrogen and-   A₁ and A₂, each one independently of the other, is derived from a    coupling component selected from the group consisting of-   an acetoacetylated amine of the formula

in which

-   X₁ represents C₁-C₄alkyl, and-   X₂ represents phenyl, which is unsubstituted, mono-, di- or    trisubstituted by SO₃H, C₁-C₄alkyl, hydroxy, C₁-C₄alkoxy, halogen or    CO₂H;-   barbituric acid or cyanoiminobarbituric acid;-   2,4,6-triaminopyrimidine;-   citrazinic acid;-   an aminopyrazole or a pyrazolone derivative of formula

in which

-   R₄ represents C₁-C₄alkyl or CO₂H,-   R₅ represents hydrogen, halogen, C₁-C₄alkyl, SO₃H or CO₂H and-   R₆ represents hydrogen;-   a benzoic acid derivative of formula

in which

-   R₇ represents hydrogen or C₁-C₄alkyl and-   R₈ represents hydrogen or hydroxy or-   A₁ and A₂, each one independently of the other, represent a phenol    residue of the formula

in which

-   R₉ represents hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, hydroxy, halogen or    SO₃H and-   R₁₀ represents hydrogen.

Most preferred compounds of formula (15) are those in which

-   R₁ represents hydrogen or C₁-C₄alkoxy, especially hydrogen,-   R₂ represents SO₃H or CO₂H, especially SO₃H,-   R₃ and R_(3a) both represent hydrogen and the coupling component A₁    is derived from an acetoacetylated amine of formula (2), barbituric    acid, cyanoiminobarbituric acid, triaminopyrimidine, citrazinic    acid, a compound of formula (5) or (7) in which R₄ represents    C₁-C₄alkyl, especially methyl, R₅ represents hydrogen or SO₃H and-   R₆ represents hydrogen or from salicyclic acid, methyl salicyclic    acid, phenol or methyl phenol and the coupling component A₂ is    derived from an acetoacetylated amine of formula (2), whereby, in    formula (2), X₁ preferably represents methyl and X₂ preferably    represents phenyl, which is monosubstituted by SO₃H or, especially,    trisubstituted by SO₃H, methyl and methoxy or A₂ is derived from an    aminopyrazole of formula (5) in which R₄ represents C₁-C₄alkyl,    especially methyl, R₅ represents hydrogen or SO₃H and R₆ represents    hydrogen.

A fourth preferred class of compounds of formula (1) is that of formula

in which

-   R₁ represents hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy or SO₃H,-   R₂ represents SO₃H or CO₂H,-   R₃ represents hydrogen, a C₁-C₄alkyl group, halogen, hydroxy,    C₁-C₄alkoxy, carboxy, NH₂ or NHC₁-C₄alkyl,-   R_(3a) represents hydrogen or NH₂ and-   A₁ and A₂ are as defined for formula (1) above.

More preferably, however, in the above compounds of formula (16),

-   R₃ and R_(3a) both represent hydrogen and-   A₁ and A₂, each one independently of the other, is derived from a    coupling component selected from the group consisting of-   an acetoacetylated amine of the formula

in which

-   X₁ represents C₁-C₄alkyl, and-   X₂ represents phenyl, which is unsubstituted, mono-, di- or    trisubstituted by SO₃H, C₁-C₄alkyl, hydroxy, C₁-C₄alkoxy, halogen or    CO₂H;-   barbituric acid or cyanoiminobarbituric acid;-   2,4,6-triaminopyrimidine;-   citrazinic acid;-   an aminopyrazole or a pyrazolone derivative of formula

in which

-   R₄ represents C₁-C₄alkyl or CO₂H,-   R₅ represents hydrogen, halogen, C₁-C₄alkyl, SO₃H or CO₂H and-   R₆ represents hydrogen;-   a benzoic acid derivative of formula

in which

-   R₇ represents hydrogen or C₁-C₄alkyl and-   R₈ represents hydrogen or hydroxy or-   A₁ and A₂, each one independently of the other, represent a phenol    residue of the formula

in which

-   R₉ represents hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, hydroxy, halogen or    SO₃H and-   R₁₀ represents hydrogen.

Most preferred compounds of formula (16) are those in which

-   R₁ represents hydrogen or C₁-C₄alkoxy, especially hydrogen,-   R₂ represents SO₃H or CO₂H, especially SO₃H,-   R₃ and R_(3a) both represent hydrogen and the coupling component A₁    is derived from an acetoacetylated amine of formula (2), barbituric    acid, cyanoiminobarbituric acid, 2,4,6-triaminopyrimidine,    citrazinic acid, a compound of formula (5) or (7) in which R₄    represents C₁-C₄alkyl, especially methyl, R₅ represents hydrogen or    SO₃H and-   R₆ represents hydrogen or from salicyclic acid, methyl salicyclic    acid, phenol or methyl phenol and the coupling component A₂ is    derived from an acetoacetylated amine of formula (2), whereby, in    formula (2), X₁ preferably represents methyl and X₂ preferably    represents phenyl, which is monosubstituted by SO₃H or, especially,    trisubstituted by SO₃H, methyl and methoxy or A₂ is derived form an    aminopyrazole of formula (5) in which R₄ represents C₁-C₄alkyl,    especially methyl, R₅ represents hydrogen or SO₃H and R₆ represents    hydrogen.

Within the scope of the definitions of the above formulae and radicals(1) to (16), a C₁-C₈alkyl radical may be branched or unbranched, forexample, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl or2-ethylhexyl.

Similarly, C₁-C₈alkoxy may be, for example, methoxy, ethoxy, n-propoxy,isopropoxy, n-butoxy, sec-butoxy, isobutoxy, t-butoxy, 2-ethylbutoxy,n-pentoxy, isopentoxy, 1-methylpentoxy, 1,3-dimethylbutoxy, n-hexyloxy,1-methylhexyloxy, n-heptyloxy, isoheptyloxy, 1,1,3,3-tetramethylbutoxy.1-methylheptyloxy, 3-methylheptyloxy, n-octyloxy or 2-ethylhexyloxy

When such alkyl or alkoxy radicals are substituted, appropriatesubstituents may typically include one or two hydroxy, SO₃H, carboxy,C₁-C₄alkoxy, hydroxy-substituted C₁-C₄alkoxy, phenyl or phenoxy groups.Suitable radicals of this type may include hydroxyethyl,1-hydroxyisopropyl, ethoxymethyl, 2-hydroxyethoxypentyl, benzyl,1-phenylethyl, 2-phenylethyl, 1-methyl-2-phenylethyl,1-isobutyl-3-phenylpropyl or 1-methyl-2-phenoxyethyl.

Halogen in the above formulae and radicals is iodine, bromine, fluorineor, especially, chlorine.

Where, in the derivatives of formulae (4) and (5), R₄ representsC₂-C₄alkenyl, this may, for example, be ethenyl, n-propenyl,isopropenyl, n-butenyl or isobutenyl.

Where, in the acetoacetylated amines of formula (2), X₂ represents a 5-or 6-membered heterocyclic ring containing 1-3 heteroatoms and which maybe benzannelated, these may be, for example, oxazol-2-yl, thiazol-2-yl,benzoxazol-2-, 5-, or 6-yl, benzothiazol-2-, 5- or 6-yl,benzimidazolone-5-yl, pyrid-2,3- or 4-yl, quinolin-2-, 4-, 5- or 6-yl or1,3,5-triazin-2-yl radicals.

The dyes of formula (1) of the invention may be prepared by knownmethods, for example by tetrazotisation of a diaminobenzanilidederivative of the formula

in which R₁, R₂, R₃ and R_(3a) are as defined for formula (1), andsequential coupling with a coupling component of the formula A₁H or A₂H,followed by coupling with a coupling component of the formula A₂H orA₁H, A₂ and A₁ being as defined for formula (1).

Such sequential coupling reactions have been described previously (see,for example, U.S. Pat. No. 5,545,725). However, it is advantageous toperform the initial coupling reaction at a pH value of between 2 and 5,especially between 2.5 and 4, whilst the subsequent coupling reaction isperformed at a pH value of between 5 and 9, preferably between 6 and 8.

The coupling components A₁H and A₂H are known compounds or may beprepared by known methods, whilst some of the diaminobenzanilides offormula (14) are novel. Consequently, further aspect of the invention isa compound of the formula

preferably 4,4′diamino-2′-methoxybenzanilide 5′-sulphonic acid or3,4′diamino-2′-methoxy-benzanilide 5′-sulphonic acid, a process for thepreparation thereof, by reaction of 2-methoxy-4-nitroaniline-5-sulphonicacid with the appropriate nitrobenzoyl halide, preferably m- orp-nitrobenzoyl chloride, followed by reduction of the resultingdinitrobenzanilide by known methods and also the use of the compound(18) for the preparation of the appropriate compound of formula (1).

The dyes of the invention may be used to dye natural or syntheticmaterials, for example, cellulosic materials, carbonamide groupcontaining materials such as polyamides, leather or glass fibres, butare particularly useful for dyeing paper. They are preferably used as asolid or liquid commercial form.

The pulverulent or granular form of the dye is used particularly inbatchwise pulp dyeing where the dye mixture, customarily in the form ofa stock solution, is added in the pulper, in the beater or in the mixingchest. Preference is here given to using dye preparations which as wellas the dye, may further include extenders, for example urea assolubilizer, dextrin, Glauber salt, sodium chloride and alsodispersants, dustproofing agents and sequestrants, such as tetrasodiumphosphate.

The present invention accordingly further provides solid dyepreparations for dyeing paper comprising a compound of the formula (1)and, optionally, further auxiliaries.

In recent years, the use of concentrated aqueous solutions of dyes hasgained importance because of the advantages possessed by such solutionswhen compared with dyes in powder form. The use of solutions avoids thedifficulties associated with dust formation and releases the user fromthe time-consuming and frequently difficult dissolving of the dye powderin water. The use of concentrated solutions was also prompted by thedevelopment of continuous dyeing processes for paper, since it isconvenient in these processes to meter the solution directly into thepulp stream or to add it at some other suitable point of thepaper-making process.

The present invention accordingly further provides aqueous solutions,preferably concentrated solutions, for dyeing paper, comprising acompound of the formula (1), preferably in a concentration of from 5 to30% by weight. Due to their excellent solubility in water, the dyes offormula (1) are particularly suitable for the preparation of suchsolutions.

The concentrated solutions preferably contain a low level of inorganicsalts, which may be achieved, if necessary, by known methods, forexample reverse osmosis.

The solutions may include further auxiliaries, for example solubilizerssuch as ε-caprolactam or urea, organic solvents, for example glycols,polyethylene glycols, dimethyl sulphoxide, N-methylpyrrolidone,acetamide, alkanolamines or polyglycolamines, which is a still furtheraspect of the invention.

In addition, the aqueous dye solutions of the present invention may beapplied to paper by use of the so-called spraying technique.

The novel dyes of the invention dye paper in predominantly yellow shadeswith excellent degrees of exhaustion with high colour strength, whilstbeing sufficiently water-soluble to provide stable aqueous formulationswithout the need for large quantities of solubilizers. Furthermore,dyings obtained exhibit high degrees of bleed- and light-fastness, areeven- or top-sided and readily bleachable.

Furthermore, as a result of their high colour strength and watersolubility, the novel dyes of the invention are suitable for use in theink-jet printing method.

Consequently, one further aspect of the invention is paper which is dyedwith a compound of the formula (1), either in the form of a solid dyepreparation, or an aqueous solution, as described above.

The following Examples serve to illustrate the invention withoutintending to be restrictive in nature. Parts and percentages are byweight unless otherwise stated.

SYNTHESIS OF INTERMEDIATE DIAMINOBENZANILIDES Example 1

73.5 g of p-phenylenediamine 2-sulphonic acid are added to 300 g ofwater and, after addition of approximately 40 g of sodium carbonate, theviolet suspension is stirred until solution results. The pH is adjustedto 7.5 by addition of concentrated hydrochloric acid and a solution of78 g of p-nitrobenzoyl chloride in 100 ml of acetone then added slowlyat 25-32° C., the pH being maintained at 6.7-7.0 by addition of 2Naqueous sodium hydroxide. After stirring for a further 1.5 hours, 210 mlof water are added and the pH adjusted to 4.0 by addition of 22 ml ofconcentrated hydrochloric acid. The readily stirrable suspension isfiltered at room temperature and washed with 200 ml of water. The filtercake is then stirred in water at 50° C., filtered hot and dried to yield75 g of 4′amino-4-nitrobenzanilide 3-sulphonic acid.

A mixture of 1300 g of water, 46.2 g of iron filings and 5.8 g ofammonium chloride is heated to boiling with vigorous stirring and thentreated with 55 g of 4′amino-4-nitrobenzanilide 3-sulphonic acid,obtained as described above. The resulting suspension is stirred for afurther 1 hour at 95-100° C. and, subsequently, cooled to roomtemperature. The suspension is filtered hot and the filtrate stirredwith 5 g of Hyflo Carcel™ for 30 minutes at room temperature. Afterfiltering, the pH of the hot filtrate is adjusted to 2.0 by addition of18 g of concentrated hydrochloric acid and the white precipitatefiltered and dried. There are obtained 39 g of 4,4′diaminobenzanilide5′-sulphonic acid of formula (100a).

Example 2

74.5 g of 2-methoxy-4-nitroaniline 5-sulphonic acid are added to 300 gof water and, after addition of approximately 30 g of sodium carbonate,the yellowish orange suspension is stirred until solution results. ThepH is adjusted to 7.0 by addition of concentrated hydrochloric acid anda solution of 60 g of p-nitrobenzoyl chloride in 75 ml of acetone thenadded slowly below 28° C., the pH being maintained at 6.7-7.0 byaddition of 2N aqueous sodium hydroxide. After stirring for a further 2hours, 650 g of water are added and the pH adjusted to 4.0 by additionof 2N aqueous hydrochloric acid. The readily stirrable suspension isfiltered, the filter cake washed with 200 g of water and sucked dry.There are obtained 391 g of damp filter cake, which is used directly forthe next step.

A mixture of 1000 g of water, 60 g of iron filings and 7.6 g of ammoniumchloride is heated to boiling with vigorous stirring and then treatedwith 145 g of the damp filter cake, obtained as described above. Theresulting suspension is stirred for a further 2 hours at 90-95° C. and,subsequently, 700 g of water are added. The suspension is filtered hotand the filtrate stirred with 10 g of Hyflo Supercel™ for 30 minutes at85° C. After filtering, the pH of the hot filtrate is adjusted to 3.8 byaddition of 24 g of concentrated hydrochloric acid and the whiteprecipitate filtered and dried. There are obtained 34.3 g of4,4′diamino-2′-methoxybenzanilide 5′-sulphonic acid of formula (100b).

Examples 3-10

By following the procedure described in Examples 1 or 2, employingappropriate starting materials, the following benzanilides may beobtained, as summarized in Table 1 below.

TABLE 1 Exam- Com- ple pound Nr. Nr Formula 3 (100c)

4 (100d)

5 (100e)

6 (100f)

7 (100g)

8 (100h)

9 (100i)

10 (100j)

Synthesis of Dyes Example 11

3.1 g of the compound of formula (100a) are suspended in 50 g of waterand 5.7 g of concentrated hydrochloric acid and subsequently treatedwith 4.75 ml of a 4N aqueous sodium nitrite solution at 0-5° C. over aperiod of 1 hour. The mixture is stirred for a further 1 hour and excessnitrite then destroyed by addition of 0.3 ml of 2N sulphamic acid. Theresultant beige suspension is diluted with 60 g of water and thentreated with a total of 2.4 g of5-amino-3-methyl-1-(3-sulphophenyl)pyrazole, in portions, at 5° C., thepH being maintained at 3.6-4.0 by addition of a total of 13.7 ml of 2Naqueous sodium hydroxide solution. The resulting monoazo suspension isthen added slowly, during 70 minutes, to a solution of 1.7 g of5-amino-3-methyl-1-phenyl pyrazole dissolved in 50 g of water and 50 gof dimethyl formamide, the pH being maintained at 6.5 by addition of atotal of 11.9 ml of 2N aqueous sodium hydroxide solution. After stirringfor a further 1.5 hours at room temperature, 50 ml of isopropanol and 30g of sodium chloride are added, the mixture stirred for 1 hour and theresulting yellowish brown suspension filtered. After drying, there areobtained 6.7 g of the compound of formula (101).

Example 12

3.1 g of the compound of formula (100a) are suspended in 50 g of waterand 5.7 g of concentrated hydrochloric acid and subsequently treatedwith 4.75 ml of a 4N aqueous sodium nitrite solution at 0-5° C. over aperiod of 1 hour. The mixture is stirred for a further 1 hour and excessnitrite then destroyed by addition of 0.3 ml of 2N sulphamic acid. Theresultant beige suspension is diluted with 60 g of water and thentreated with 1.75 g of 5-amino-3-methyl-1-phenyl pyrazole and reactioncontinued for 2.5 hours at 5° C., the pH being maintained at 3.8-4.0 byaddition of a total of 15.9 ml of 2N aqueous sodium hydroxide solution.The resulting monoazo suspension is then added slowly, during 2.5 hours,to a solution of 3.0 g of 3-acetoacetylamino-4-methoxy toluene6-sulphonic acid dissolved in 50 g of water and 50 g of dimethylformamide, the pH being maintained at 6.8 by addition of a total of 7 mlof 2N aqueous sodium hydroxide solution. After stirring for a further1.5 hours at 30-35° C., 75 ml of isopropanol and 45 g of sodium chlorideare added and the resulting yellow suspension filtered. After drying,there are obtained 6.8 g of the compound of formula (102).

Example 13

3.1 g of the compound of formula (100a) are suspended in 50 g of waterand 5.7 g of concentrated hydrochloric acid and subsequently treatedwith 4.75 ml of a 4N aqueous sodium nitrite solution at 0-5° C. over aperiod of 1 hour. The mixture is stirred for a further 1 hour and excessnitrite then destroyed by addition of 0.3 ml of 2N sulphamic acid. Theresultant beige suspension is diluted with 60 g of water and thentreated with 1.2 g of barbituric acid. The pH is raised to 2.5 and thenmaintained at 2.3-2.5 over a period of 3 hours by addition of a total of5.1 ml of 4N aqueous sodium hydroxide solution. The resulting monoazosuspension is then added slowly, during 1.5 hours, to a solution of 3.5g of 3-acetoacetylamino-4-methoxy toluene 6-sulphonic acid dissolved in100 g of water, the pH being maintained at 6.5 by addition of a total of5.4 ml of 4N aqueous sodium hydroxide solution. After stirring for afurther 2.5 hours at room temperature, 75 ml of isopropanol and 15 g ofsodium chloride are added and, after stirring briefly at roomtemperature, the resulting yellowish red suspension is filtered. Afterdrying, there are obtained 7.1 g of the compound of formula (103).

Example 14

3.1 g of the compound of formula (100a) are suspended in 50 g of waterand 5.7 g of concentrated hydrochloric acid and subsequently treatedwith 4.75 ml of a 4N aqueous sodium nitrite solution at 0-5° C. over aperiod of 1 hour. The mixture is stirred for a further 1 hour and excessnitrite then destroyed by addition of 0.3 ml of 2N sulphamic acid. Theresultant beige suspension is filtered and the moist presscake suspendedin 110 ml of water. 1.75 g of 3-methyl-1-phenyl pyrazo-2-one are addedand the pH raised to 3.7. By the addition of a total of 2.5 ml of 4Naqueous sodium hydroxide solution, the pH is maintained at 3.5-4.0,whilst the temperature is raised stepwise from 10° C. to 30° C. Afterstirring for a total of 3.5 hours the coupling reaction is complete. Tothe resulting monoazo suspension are then added 50 g of dimethylformamide followed by 3.5 g of 3-acetoacetylamino-4-methoxy toluene6-sulphonic acid. The pH is adjusted to 7.0-7.5 and maintained at thisvalue by addition of a further 2.7 ml of 4N aqueous sodium hydroxidesolution. After stirring for a further 2 hours at room temperature, 20 gof sodium chloride are added, the mixture stirred for 1 hour at roomtemperature and the resulting yellow suspension filtered. After drying,there are obtained 5.5 g of the compound of formula (104).

Example 15

3.1 g of the compound of formula (100a) are suspended in 50 g of waterand 5.7 g of concentrated hydrochloric acid and subsequently treatedwith 4.75 ml of a 4N aqueous sodium nitrite solution at 0-5° C. over aperiod of 1 hour. The mixture is stirred for a further 1 hour and excessnitrite then destroyed by addition of 0.3 ml of 2N sulphamic acid. Theresultant beige suspension is filtered and the moist presscake suspendedin 110 ml of water. 1.4 g of salicylic acid are added and the pH raisedto 3.0-3.3. By the addition of a total of 4.9 ml of 2N aqueous sodiumhydroxide solution, the pH is maintained at 3.0-3.5. After stirring fora total of 2.5 hours at room temperature the coupling reaction iscomplete. To the resulting monoazo suspension are then added 3.5 g of3-acetoacetylamino-4-methoxy toluene 6-sulphonic acid. The pH isadjusted to 6.5 and maintained at this value by addition of a further4.9 ml of 2N aqueous sodium hydroxide solution. After stirring for atotal of 3.5 hours at room temperature, 10 g of sodium chloride and 15ml of isopropanol are added, the pH increased to 8.5 and the resultingyellowish brown suspension filtered. After drying, there are obtained5.2 g of the compound of formula (105).

Examples 16-116

By proceeding in an analogous manner to that described in Examples11-15, but utilizing the appropriate coupling components, compounds offormula (19) are obtained, as summarized in the following Table 2.

TABLE 2 (19)

Example Nr. Compound Nr. A′₁ A′₂ 16 (106)

17 (107)

18 (108)

19 (109)

20 (110)

21 (111)

22 (112)

23 (113)

24 (114)

25 (115)

26 (116)

27 (117)

28 (118)

29 (119)

30 (120)

31 (121)

32 (122)

33 (123)

34 (124)

35 (125)

36 (126)

37 (127)

38 (128)

39 (129)

40 (130)

41 (131)

42 (132)

43 (133)

44 (134)

45 (135)

46 (136)

47 (137)

48 (138)

49 (139)

50 (140)

51 (141)

52 (142)

53 (143)

54 (144)

55 (145)

56 (146)

57 (147)

58 (148)

59 (149)

60 (150)

61 (151)

62 (152)

63 (153)

64 (154)

65 (155)

66 (156)

67 (157)

68 (158)

69 (159)

70 (160)

71 (161)

72 (162)

73 (163)

74 (164)

75 (165)

76 (166)

77 (167)

78 (168)

79 (169)

80 (170)

81 (171)

82 (172)

83 (173)

84 (174)

85 (175)

86 (176)

87 (177)

88 (178)

89 (179)

90 (180)

91 (181)

92 (182)

93 (183)

94 (184)

95 (185)

96 (186)

97 (187)

98 (188)

99 (189)

100 (190)

101 (191)

102 (192)

103 (193)

104 (194)

105 (195)

106 (196)

107 (197)

108 (198)

109 (199)

110 (200)

111 (201)

112 (202)

113 (203)

114 (204)

115 (205)

116 (206)

117 (207)

118 (208)

119 (209)

120 (210)

121 (211)

122 (212)

123 (213)

Example 124

4.5 g of 4,4′diamino-2′-methoxybenzanilide 5′-sulphonic acid of formula(100b), prepared as described in Example 2, are suspended in 50 g ofwater and 7.6 g of concentrated hydrochloric acid and subsequentlytreated with 5.7 ml of 4N aqueous sodium nitrite solution over 1 hour at0-5° C. The mixture is stirred for a further 1 hour and excess nitritedestroyed by addition of 0.8 ml of 2N aqueous sulphamic acid solution.The resulting yellow suspension is diluted with 60 g of water andtreated with 2.9 g of 5-amino-3-methyl-1-(3-sulphophenyl)pyrazole at 5°C., the pH being initially raised to 3.5 and maintained at 3.0-3-5 bythe addition of a total of 27.4 ml of 2N aqueous sodium hydroxidesolution. After stirring for 2.5 hours the initial coupling reaction iscompleted. The resulting monoazo suspension is slowly added to asolution of 4.0 g of 3-acetacetylamino-4-methoxytoluene 6-sulphonic acidin 50 g of dimethylformamide over 2.5 hours at 30° C., the pH beingmaintained at 6.8-7.0 by addition of a total of 7.3 ml of 4N aqueoussodium hydroxide solution. After stirring for 1.5 hours at 30° C., 35 gof sodium chloride and 50 g of isopropanol are added, the mixturestirred over night and the precipitated solids filtered. After drying,there are obtained 10.2 g of the compound of formula (214).

Example 125

4.5 g of 4,4′diamino-2′-methoxybenzanilide 5′-sulphonic acid of formula(100b), prepared as described in Example 2, are suspended in 50 g ofwater and 7.6 g of concentrated hydrochloric acid and subsequentlytreated with 5.7 ml of 4N aqueous sodium nitrite solution over 1 hour at0-5° C. The mixture is stirred for a further 1 hour and excess nitritedestroyed by addition of 0.8 ml of 2N aqueous sulphamic acid solution.The resulting yellow suspension is added to a solution of 7.7 g of3-acetacetylamino-4-methoxytoluene 6-sulphonic acid in 100 g of waterover 30 minutes at 5° C., the pH being of which is initially adjusted to3.8 and is maintained at 3.8-4.0 by the addition of a total of 22.6 mlof 2N aqueous sodium hydroxide solution. Subsequently, the pH is raisedto 6.8-7.4 by addition of a further 10.1 ml of 2N aqueous sodiumhydroxide solution and the temperature increased to 25-40° C. Afterstirring for a total of 3 hours, 45 g of potassium chloride and 50 g ofisopropanol are added and the precipitated solids filtered. Afterdrying, there are obtained 12.9 g of the compound of formula (215).

Example 126

2.1 g of 4,4′diamino-2′-methoxybenzanilide 5′-sulphonic acid of formula(100b), prepared as described in Example 2, are suspended in 50 g ofwater and 7.6 g of concentrated hydrochloric acid and subsequentlytreated with 5.7 ml of 4N aqueous sodium nitrite solution over 1 hour at0-5° C. The mixture is stirred for a further 1 hour and excess nitritedestroyed by addition of 2N aqueous sulphamic acid solution. Theresulting yellow solution is treated with 0.9 g of5-amino-3-methyl-1-phenyl pyrazole at 5° C., the pH being initiallyraised to 3.0 and maintained at 2.5-3.0 by the addition of a total of3.1 ml of 4N aqueous sodium hydroxide solution. After stirring for 2.5hours and slowly warming to 20° C., the initial coupling reaction iscompleted. To the resulting monoazo suspension are added 1.7 g of3-acetacetylamino-4-methoxytoluene 6-sulphonic acid, the pH raised to6.5 and maintained at 6.0-7.5 by addition of a total of 2.2 ml of 4Naqueous sodium hydroxide solution. After stirring for 3 hours at 20-40°C. reaction is complete and the precipitated solids are filtered. Afterdrying, there are obtained 5.4 g of the compound of formula (216).

Examples 127-198

By proceeding in an analogous manner to that described in Examples124-126, but utilizing the appropriate coupling components, compounds offormula (20) are obtained, as summarized in the following Table 3.

TABLE 3 (20)

Example Nr. Compound Nr. A′₁ A′₂ 127 (217)

128 (218)

129 (219)

130 (220)

131 (221)

132 (222)

133 (223)

134 (224)

135 (225)

136 (226)

137 (227)

138 (228)

139 (229)

140 (230)

141 (231)

142 (232)

143 (233)

144 (234)

145 (235)

146 (236)

147 (237)

148 (238)

149 (239)

150 (240)

151 (241)

152 (242)

153 (243)

154 (244)

155 (245)

156 (246)

157 (247)

158 (248)

159 (249)

160 (250)

161 (251)

162 (252)

163 (253)

164 (254)

165 (255)

166 (256)

167 (257)

168 (258)

169 (259)

170 (260)

171 (261)

172 (262)

173 (263)

174 (264)

175 (265)

176 (266)

177 (267)

178 (268)

179 (269)

180 (270)

181 (271)

182 (272)

183 (273)

184 (274)

185 (275)

186 (276)

187 (277)

188 (278)

189 (279)

190 (280)

191 (281)

192 (282)

193 (283)

194 (284)

195 (285)

196 (286)

197 (287)

198 (288)

Examples 199-217

By proceeding in an analogous manner to that described in Examples11-15, but replacing the compound of formula (100a) by the compound offormula (100c) and utilizing the appropriate coupling components,compounds of formula (21) are obtained, as summarized in the followingTable 4.

TABLE 4 (21)

Example Nr. Compound Nr. A′₁ A′₂ 199 (289)

200 (290)

201 (291)

202 (292)

203 (293)

204 (294)

205 (295)

206 (296)

207 (297)

208 (298)

209 (299)

210 (300)

211 (301)

212 (302)

213 (303)

214 (304)

215 (305)

216 (306)

217 (307)

Examples 218-236

By proceeding in an analogous manner to that described in Examples124-126, but replacing the compound of formula (100b) by the compound offormula (100d) and utilizing the appropriate coupling components,compounds of formula (22) are obtained, as summarized in the followingTable 5.

TABLE 5 (22)

Example Nr. Compound Nr. A′₁ A′₂ 218 (308)

219 (309)

220 (310)

221 (311)

222 (312)

223 (313)

224 (314)

225 (315)

226 (316)

227 (317)

228 (318)

229 (319)

230 (320)

231 (321)

232 (322)

233 (323)

234 (324)

235 (325)

236 (326)

Examples 237-255

By proceeding in an analogous manner to that described in Examples11-15, but replacing the compound of formula (100a) by the compound offormula (100e) and utilizing the appropriate coupling components,compounds of formula (23) are obtained, as summarized in the followingTable 6.

TABLE 6 (23)

Example Nr. Compound Nr. A′₁ A′₂ 237 (327)

238 (328)

239 (329)

240 (330)

241 (331)

242 (332)

243 (333)

244 (334)

245 (335)

246 (336)

247 (337)

248 (338)

249 (339)

250 (340)

251 (341)

252 (342)

253 (343)

254 (344)

255 (345)

Examples 256-274

By proceeding in an analogous manner to that described in Examples11-15, but replacing the compound of formula (100a) by the compound offormula (100f) and utilizing the appropriate coupling components,compounds of formula (24) are obtained, as summarized in the followingTable 7.

TABLE 7 (24)

Example Nr. Compound Nr. A′₁ A′₂ 256 (346)

257 (347)

258 (348)

259 (349)

260 (350)

261 (351)

262 (352)

263 (353)

264 (354)

265 (355)

266 (356)

267 (357)

268 (358)

269 (359)

270 (360)

271 (361)

272 (362)

273 (363)

274 (364)

Examples 275-286

By proceeding in an analogous manner to that described in Examples11-15, but replacing the compound of formula (100a) by the compound offormula (100 g) and utilizing the appropriate coupling components,compounds of formula (25) are obtained, as summarized in the followingTable 8.

TABLE 8 (25)

Example Nr. Compound Nr. A′₁ A′₂ 275 (365)

276 (366)

277 (367)

278 (368)

279 (369)

280 (370)

281 (371)

282 (372)

283 (373)

284 (374)

285 (375)

286 (376)

Examples 287-298

By proceeding in an analogous manner to that described in Examples11-15, but replacing the compound of formula (100a) by the compound offormula (100h) and utilizing the appropriate coupling components,compounds of formula (26) are obtained, as summarized in the followingTable 9.

TABLE 9 (26)

Example Nr. Compound Nr. A′₁ A′₂ 287 (377)

288 (378)

289 (379)

290 (380)

291 (381)

292 (382)

293 (383)

294 (384)

295 (385)

296 (386)

297 (387)

298 (388)

Examples 299-365

By proceeding in an analogous manner to that described in Examples11-15, but replacing the compound of formula (100a) by the compound offormula (100i) and utilizing the appropriate coupling components,compounds of formula (27) are obtained, as summarized in the followingTable 10.

TABLE 10 (27)

Example Nr. Compound Nr. A′₁ A′₂ 299 (389)

300 (390)

301 (391)

302 (392)

303 (393)

304 (394)

305 (395)

306 (396)

307 (397)

308 (398)

309 (399)

310 (340)

311 (401)

312 (402)

313 (403)

314 (404)

315 (405)

316 (406)

317 (407)

318 (408)

319 (409)

320 (410)

321 (411)

322 (412)

323 (413)

324 (414)

325 (415)

326 (416)

327 (417)

328 (418)

329 (419)

330 (420)

331 (421)

332 (422)

333 (423)

334 (424)

335 (425)

336 (426)

337 (427)

338 (428)

339 (429)

340 (430)

341 (431)

342 (432)

343 (433)

344 (434)

345 (435)

346 (436)

347 (437)

348 (438)

349 (439)

350 (440)

351 (441)

352 (442)

353 (443)

354 (444)

355 (445)

356 (446)

357 (447)

358 (448)

359 (449)

360 (450)

361 (451)

362 (452)

363 (453)

364 (454)

365 (455)

Examples 366-436

By proceeding in an analogous manner to that described in Examples11-15, but replacing the compound of formula (100a) by the compound offormula (100J) and utilizing the appropriate coupling components,compounds of formula (28) are obtained, as summarized in the followingTable 11.

TABLE 11 (28)

Example Nr. Compound Nr. A′₁ A′₂ 366 (456)

367 (457)

368 (458)

369 (459)

370 (460)

371 (461)

372 (462)

373 (463)

374 (464)

375 (465)

376 (466)

377 (467)

378 (468)

379 (469)

380 (470)

381 (471)

382 (472)

383 (473)

384 (474)

385 (475)

386 (476)

387 (477)

388 (478)

389 (479)

390 (480)

391 (481)

392 (482)

393 (483)

394 (484)

395 (485)

396 (486)

397 (487)

398 (488)

399 (489)

400 (490)

401 (491)

402 (492)

403 (493)

404 (494)

405 (495)

406 (496)

407 (497)

408 (498)

409 (499)

410 (500)

411 (501)

412 (502)

413 (503)

414 (504)

415 (505)

416 (506)

417 (507)

418 (508)

419 (509)

420 (510)

421 (511)

422 (512)

423 (513)

424 (514)

425 (515)

426 (516)

427 (517)

428 (518)

429 (519)

430 (520)

431 (521)

432 (522)

433 (523)

434 (524)

435 (525)

436 (526)

Application Examples Example 437 Unsized without Filler

A mixture consisting of 50% long fibre spruce sulphite bleached and 50%short fibre beech sulphite bleached fibres is suspended in deionisedwater, as a 2% suspension, and refined and beaten to 22° SR (SchopperRiegler). After dewatering by means of a centrifuge and testing for dryweight, the equivalent to 10 g of dry fibre are placed in a beaker andmade up to a volume of 500 ml with tap water. After stirring for 1 hour,0.42%, based on the weight of dry fibre, of compound (101) as a 5 g/laqueous solution are added to the furnish suspension and stirringcontinued for a further 15 minutes. The suspension is made up to 700 mlwith water and from 300 ml of the resulting suspension a hand sheet isproduced using a Lhomargy sheet former. After drying on a cylinder at90° C. for 12 minutes, a greenish-yellow dyeing is obtained showingexcellent bleed-fastness to water, soda and acetic acid and goodlight-fastness. The backwater from the dyeing is almost colourless andthe degree of exhaustion amounts to 92-94%.

Examples 438-455

The procedure described in Example 437 is repeated using, instead ofcompound (101), sufficient amounts of the appropriate dye to produce adyeing of standard depth 0.2. The degrees of exhaustion of therespective dyes are calculated and the results summarized in Table 12below.

TABLE 12 Example Nr. Compound Nr. Degree of Exhaustion in % 438 (102) 98439 (103) 98 440 (104) 92-94 441 (105) 98-99 442 (106) 93-94 443 (107)93 444 (108) 92 445 (110) 98 446 (135) 97-98 447 (151) 95 448 (157)98-99 449 (189) 95 450 (190)   97.5 451 (200)   96.5 452 (205) 97 453(214) 95-97 453 (216) 97-98 454 (267) 93 455 (288) 98

The above results clearly demonstrate the excellent degrees ofexhaustion of the dyes tested, the backwater, in all cases, being almostcolourless.

Example 456 Neutral Sized with Filler

A mixture consisting of 50% long fibre spruce sulphite bleached and 50%short fibre beech sulphite bleached fibres is suspended in deionisedwater, as a 2% suspension, and refined and beaten to 35° SR (SchopperRiegler). After dewatering by means of a centrifuge and testing for dryweight, the equivalent to 10 g of dry fibre and 2 g of dry chalk fillerare placed in a beaker and made up to a volume of 500 ml with tap water.After stirring for 1 hour, 0.78%, based on the weight of dry fibre, ofcompound (101) as a 5 g/l aqueous solution are added to the furnishsuspension and stirring continued for a further 15 minutes. 2% of alkylketene dimer size is then added, the suspension stirred for 30 minutes,0.05% retention aid added and the suspension stirred vigorously for afurther 5 minutes. The suspension is made up to 700 ml with water andfrom 300 ml of the resulting suspension a hand sheet is produced using aLhomargy sheet former. After drying on a cylinder at 90° C. for 12minutes, a greenish-yellow dyeing is obtained showing excellent fastnessvalues. The backwater from the dyeing is only weakly coloured.

1. A compound of formula (14) or (16)

wherein R₁ represents hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy or SO₃H, R₂represents SO₃H or CO₂H, R₃ represents hydrogen, C₁-C₄alkyl, halogen,hydroxy, C₁-C₄alkoxy, carboxy, NH₂ or NHC₁-C₄alkyl, R_(3a) representshydrogen or NH₂ and A₁ and A₂ are independently selected from the groupconsisting of an acetoacetylated amine of formula (2)

wherein X₁ represents C₁-C₄alkyl, or phenyl which is unsubstituted ormonosubstituted by C₁-C₄alkyl, C₁-C₄alkoxy or halogen and X₂ representsphenyl which is unsubstituted, mono-, di- or trisubstituted by one ortwo SO₃H, SO₂NHC₁-C₄ alkyl groups which alkyl groups may be substituted,SO₂C₁-C₄alkyl, C₁-C₄substituted or unsubstituted alkyl, hydroxy,C₁-C₄alkoxy, halogen, CF₃, NH₂, NHCOC₁-C₄alkyl, NHCOOC₁-C₄alkyl,NHCONHC₁-C₄alkyl, CO₂H, CONHC₁-C₄alkyl or NO₂; a 1- or 2-naphthylresidue which is unsubstituted or substituted by one or two SO₃H,SO₂NHC₁-C₄alkyl, carboxy, CONHC₁-C₄alkyl, carboxyC₁-C₄alkyl orcarboxyaryl groups or a 5- or 6-membered heterocyclic ring containing1-3 heteroatoms and which may be benzannelated and be furthersubstituted by C₁-C₄alkyl, C₁-C₄alkoxy or halogen and which may beattached to the NH-atom in formula (2) either via the hetero- orbenzo-nucleus, in the case of benzannelated heterocycles; a derivativeof barbituric acid of formula (3)

wherein Y represents O, NCN or NCONH₂; a 2,4,6-triaminopyrimidine; apyridone derivative of formula (4)

wherein Q₁ represents hydrogen, hydroxy, C₁-C₂alkyl, hydroxyethyl,2-(C₁-C₂alkoxy)alkyl, C₁-C₂alkoxy, COOH, CONH₂ or COOC₁-C₂alkyl, Q₂represents hydrogen, CN, CONH₂, halogen, SO₃H or C₁-C₂alkyl which isunsubstituted or substituted by hydroxy, phenyl or SO₃H, Q₃ representshydrogen, phenyl, C₁-C₂alkylphenyl, cyclohexyl or C₁-C₄alkyl which isunsubstituted or substituted by hydroxy, CN, C₁-C₂alkoxy or SO₃H and Q₄represents hydrogen or hydroxy; an aminopyrazole or a pyrazolonederivative of formula (6), (7) or (8)

wherein R₄ represents hydrogen, substituted or unsubstituted C₁-C₄alkyl,C₂-C₄alkenyl, NHCOC₁-C₄alkyl, or CO₂H, each R₅ and R₆, independently ofthe other, represent hydrogen, halogen, C₁-C₄alkyl, SO₃H, or CO₂H and R₇represents hydrogen or C₁-C₄alkyl; a benzoic acid derivative of formula(9) or (10)

wherein R₇ represents hydrogen or C₁-C₄alkyl and R₈ represents hydrogenor hydroxy; and a phenol residue of formula (11) or (12)

wherein R₉ and R₁₀, each one independently of the other, representhydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, hydroxy, halogen, NH₂, NHCOC₁-C₄alkyl, NO₂, SO₃H, CO₂C₁-C₄alkyl or CONHC₁-C₄alkyl groups, providedthat in compounds of formula (14) if R₂ represents CO₂H, R₃ representshydroxy or methoxy, and R_(3a) represents hydrogen, then A₁ and A₂ donot represent residues of formulae (2) or (7); and in compounds offormula (16) if R₂ represents SO₃H and R₃ and R_(3a) both representhydrogen, then A₁ and A₂ are not both 2,4-dihydroxyphenyl.
 2. Thecompound of formula (14) according to claim 1, wherein, R₃ and R_(3a)both represent hydrogen and A₁ and A₂, are independently selected fromthe group consisting of an acetoacetylated amine of formula (2)

wherein X₁ represents C₁-C₄alkyl, and X₂ represents phenyl, which isunsubstituted, mono-, di- or trisubstituted by SO₃H, C₁-C₄alkyl,hydroxy, C₁-C₄alkoxy, halogen or CO₂H; barbituric acid,cyanoiminobarbituric acid; 2,4,6-triaminopyrimidine; citrazinic acid; apyrazolone derivative of formula (7)

wherein R₄ represents C₁-C₄alkyl or CO₂H, R₅ represents hydrogen,halogen, C₁-C₄alkyl, SO₃H or CO₂H and R₆ represents hydrogen; a benzoicacid derivative of formula (9) or (10)

wherein R₇ represents hydrogen or C₁-C₄alkyl and R₈ represents hydrogenor hydroxy; and a phenol residue of formula (11) or (12)

wherein R₉ represents hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, hydroxy,halogen or SO₃H and R₁₀ represents hydrogen.
 3. The compound of formula(16) according to claim 1, wherein R₃ and R_(3a) both represent hydrogenand A₁ and A₂ are independently selected from the group consisting of anacetoacetylated amine of formula (2)

wherein X₁ represents C₁-C₄alkyl, and X₂ represents phenyl, which isunsubstituted, mono-, di- or trisubstituted by SO₃H, C₁-C₄alkyl,hydroxy, C₁-C₄alkoxy, halogen or CO₂H; barbituric acid;cyanoiminobarbituric acid; 2,4,6-triaminopyrimidine; citrazinic acid; apyrazolone derivative of formula (7)

wherein R₄ represents C₁-C₄alkyl or CO₂H, R₅ represents hydrogen,halogen, C₁-C₄alkyl, SO₃H or CO₂H and R₆ represents hydrogen; a benzoicacid derivative of formula (9) or (10)

wherein R₇ represents hydrogen or C₁-C₄alkyl and R₈ represents hydrogenor hydroxy; and a phenol residue of formula (11) or (12)

wherein R₉ represents hydrogen, C₁-C₄alkyl, C₁-C₄alkoxy, hydroxy,halogen or SO₃H and R₁₀ represents hydrogen.
 4. A process for thepreparation of a compound of formula (14) or (16) according to claim 1,said process comprising forming a bis-diazo compound by tetrazotisationof a diaminobenzanilide of formula (17)

wherein R₁, R₂, R₃ and R_(3a) are as defined in claim 1; coupling saidbis-diazo compound with a coupling component of formula A₁H or A₂H toform a monoazo compound; and coupling said monoazo compound with acoupling component of formula A₂H or A₁H, A₂ and A₁ being as defined inclaim
 1. 5. A solid dye preparation for dyeing paper, said dyepreparation comprising a compound of formula (14) or (16) according toclaim 1, and, optionally, further auxiliaries.
 6. An aqueous solutionfor dyeing paper, said solution comprising a compound of formula (14) or(16) according to claim 1, and, optionally, further auxiliaries.
 7. Theaqueous solutions according to claim 6, wherein said further auxiliariesare solubilizers and/or organic solvents.
 8. A paper dyed with acompound of formula (14) or (16) according to claim
 1. 9. A process forthe preparation of a compound of formula (14) or (16) according to claim1, said process comprising forming a bis-diazo compound bytetrazotisation of a diaminobenzanilide of formula (17)

wherein R₁, R₂, R₃ and R_(3a) are as defined in claim 1; and couplingsaid bis-diazo compound with a coupling component of formula A₁H or A₂H.